English

Defective Ultrathin Two-Dimensional Materials for Photo-/Electrocatalytic CO₂ Reduction: Fundamentals and Perspectives

• Runhua Chen ^{1, †,} ,
• Qiong Wu ^{1, †,} ,
• Jingchen Luo ^1, ,
• Xiaolong Zu ^{2, ,} ,
• Shan Zhu ^3, ,
• Yongfu Sun ^{1, ,}

• 1.

  Hefei National Research Center for Physical Sciences at Microscale, University of Science and Technology of China, Hefei 230026, China

• 2.

  Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province (IKKEM), Xiamen 361005, Fujian Province, China

• 3.

  State Grid Anhui Electric Power Research Institute, Hefei 230601, China

Corresponding author: Xiaolong Zu, xiaolongzu@xmu.edu.cn; Yongfu Sun, yfsun@ustc.edu.cn

• Received Date: 31 August 2023
  Accepted Date: 17 October 2023
  Revised Date: 04 October 2023
  Available Online: 15 March 2025
• Fund Project:

  the National Key Research and Development Program of China 

  the National Key Research and Development Program of China 

  the National Key Research and Development Program of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the National Natural Science Foundation of China 

  the Youth Innovation Promotion Association of CAS 

  the Anhui Provincial Natural Science Foundation 

Abstract: Photo-/electrocatalytic reduction of carbon dioxide (CO₂) to carbon-based fuel molecules driven by renewable energy is an attractive strategy for resource regeneration and energy storage, especially for achieving carbon peak and carbon-neutral goals. However, the high thermodynamic stability and chemical inertness of CO₂ molecules make the conversion efficiency and selectivity of reduction products very low, which further hinders its application. In addition, different CO₂ reduction products have similar reduction potential and usually face severe hydrogen evolution competition under aqueous system conditions, which makes the selectivity of specific reduction products unable to be effectively controlled. To overcome these bottlenecks, researchers have been working for many years to develop efficient photo/electrocatalysts to enhance the activity and product selectivity of CO₂ reduction. Thanks to the ultrathin thickness and large specific surface area, ultrathin two-dimensional materials possess highly active sites with high density and high uniformity, which can effectively regulate the key thermodynamic and kinetic factors of CO₂ photo-/electroreduction reactions. As a typical two-dimensional material, the defective ultrathin two-dimensional materials can provide a large number of electron-rich catalytic sites to efficiently adsorb and highly activate CO₂ molecules, which can effectively reduce the reaction barrier, thus accelerating CO₂ reduction and enhancing product selectivity. Moreover, the local atomic and electronic structure of the defects can effectively stabilize the intermediate of CO₂ reduction reactions, thus further optimizing the kinetics of CO₂ reduction reactions. Furthermore, the surface defects are beneficial to the mass and electron transfer in the catalytic process, thus further improving the catalytic activity of the catalysts. In this review, we overview the latest research progress in CO₂ photo-/electrocatalytic reduction using defective ultrathin two-dimensional materials, including the controllable synthesis and fine structure characterization of defective ultrathin two-dimensional materials; the modulation effect of defect structure on the local atomic and electronic structure; the advantages of defective ultrathin two-dimensional materials for CO₂ reduction. We also discuss the challenges and opportunities of defective ultrathin two-dimensional materials for future development of CO₂ photo-/electrocatalytic reduction. It is expected that this review will provide a guide for designing highly efficient CO₂ reduction systems.

Key words:
• Defect
•  /  Ultrathin two-dimensional materials
•  /  CO₂ reduction
•  /  Photo-/Electrocatalysis

• 1. [1]

     Aresta, M.; Dibenedetto, A.; Angelini, A. Chem. Rev. 2014, 114, 1709. doi: 10.1021/cr4002758

  2. [2]

     Gao, S.; Lin, Y.; Jiao, X.; Sun, Y.; Luo, Q.; Zhang, W.; Li, D.; Yang, J.; Xie, Y. Nature 2016, 529, 68. doi: 10.1038/nature16455

  3. [3]

     Li, Y.; Li, F.; Laaksonen, A.; Wang, C.; Cobden, P.; Boden, P.; Liu, Y.; Zhang, X.; Ji, X. Ind. Chem. Mater. 2023, 1, 410. doi: 10.1039/D2IM00055E

  4. [4]

     Jiang, J.; Xiong, Z.; Wang, H.; Liao, G.; Bai, S.; Zou, J.; Wu, P.; Zhang, P.; Li, X. J. Mater. Sci. Technol. 2022, 118, 15. doi: 10.1016/j.jmst.2021.12.018

  5. [5]

     Wu, Y.; Wu, M.; Zhu, J.; Zhang, X.; Li, J.; Zheng, K.; Hu, J.; Liu, C.; Pan, Y.; Zhu, J.; et al. Sci. China Chem. 2023, 66, 1997. doi: 10.1007/s11426-022-1595-9

  6. [6]

     常诚, 陈伟, 陈也, 陈永华, 陈雨, 丁峰, 樊春海, 范红金, 范战西, 龚成, 等. 物理化学学报, 2021, 37, 2108017. ] doi: 10.3866/PKU.WHXB202108017Chang, C.; Chen, W.; Chen, Y.; Chen, Y. H.; Chen, Y.; Ding, F.; Fan, C. H.; Fan, H. J.; Fan, Z. X.; Gong, C.; et al. Acta Phys. -Chim. Sin. 2021, 37, 2108017. doi: 10.3866/PKU.WHXB202108017

  7. [7]

     Bai, S.; Zhang, N.; Gao, C.; Xiong, Y. Nano Energy 2018, 53, 296. doi: 10.1016/j.nanoen.2018.08.058

  8. [8]

     Sun, Y.; Gao, S.; Lei, F.; Xie, Y. Chem. Soc. Rev. 2015, 44, 623. doi: 10.1039/C4CS00236A

  9. [9]

     Wang, Y.; Liu, J.; Zheng, G. Adv. Mater. 2021, 33, 2005798. doi: 10.1002/adma.202005798

  10. [10]

      Zhou, W.; Fu, H. Inorg. Chem. Front. 2018, 5, 1240. doi: 10.1039/C8QI00122G

  11. [11]

      Jiang, J.; Li, F.; Bai, S.; Wang, Y.; Xiang, K.; Wang, H.; Zou, J.; Hsu, J. -P. Nano Res. 2023, 16, 4656. doi: 10.1007/s12274-022-5112-x

  12. [12]

      Jiang, J.; Ou-yang, L.; Zhu, L.; Zheng, A.; Zou, J.; Yi, X.; Tang, H. Carbon 2014, 80, 213. doi: 10.1016/j.carbon.2014.08.059

  13. [13]

      Zou, J.; Wu, S.; Liu, Y.; Sun, Y.; Cao, Y.; Hsu, J. -P.; Shen Wee, A. T.; Jiang, J. Carbon 2018, 130, 652. doi: 10.1016/j.carbon.2018.01.008

  14. [14]

      Jiao, X.; Hu, Z.; Li, L.; Wu, Y.; Zheng, K.; Sun, Y.; Xie, Y. Sci. China Chem. 2022, 65, 428. doi: 10.1007/s11426-021-1184-6

  15. [15]

      Li, X.; Wang, S.; Li, L.; Sun, Y.; Xie, Y. J. Am. Chem. Soc. 2020, 142, 9567. doi: 10.1021/jacs.0c02973

  16. [16]

      Corma, A.; Garcia, H. J. Catal. 2013, 308, 168. doi: 10.1016/j.jcat.2013.06.008

  17. [17]

      Nitopi, S.; Bertheussen, E.; Scott, S. B.; Liu, X.; Engstfeld, A. K.; Horch, S.; Seger, B.; Stephens, I. E. L.; Chan, K.; Hahn, C.; et al. Chem. Rev. 2019, 119, 7610. doi: 10.1021/acs.chemrev.8b00705

  18. [18]

      Chang, X.; Wang, T.; Gong, J. Energy Environ. Sci. 2016, 9, 2177. doi: 10.1039/C6EE00383D

  19. [19]

      Ménard, G.; Stephan, D. W. Angew. Chem. Int. Ed. 2011, 50, 8396. doi: 10.1002/anie.201103600

  20. [20]

      陈瑶, 陈存, 曹雪松, 王震宇, 张楠, 刘天西. 物理化学学报, 2023, 39, 2212053. ] doi: 10.3866/PKU.WHXB202212053Chen, Y.; Chen, C.; Cao, X. S.; Wang, Z. Y.; Zhang, N.; Liu, T. X. Acta Phys. -Chim. Sin. 2023, 39, 2212053. doi: 10.3866/PKU.WHXB202212053

  21. [21]

      Sun, Z.; Ma, T.; Tao, H.; Fan, Q.; Han, B. Chem 2017, 3, 560. doi: 10.1016/j.chempr.2017.09.009

  22. [22]

      Zhou, Y.; Wang, Z.; Huang, L.; Zaman, S.; Lei, K.; Yue, T.; Li, Z. A.; You, B.; Xia, B. Y. Adv. Energy Mater. 2021, 11, 2003159. doi: 10.1002/aenm.202003159

  23. [23]

      Zhao, Y.; Chen, G.; Bian, T.; Zhou, C.; Waterhouse, G. I. N.; Wu, L. -Z.; Tung, C. -H.; Smith, L. J.; O'Hare, D.; Zhang, T. Adv. Mater. 2015, 27, 7824. doi: 10.1002/adma.201503730

  24. [24]

      Guan, M.; Xiao, C.; Zhang, J.; Fan, S.; An, R.; Cheng, Q.; Xie, J.; Zhou, M.; Ye, B.; Xie, Y. J. Am. Chem. Soc. 2013, 135, 10411. doi: 10.1021/ja402956f

  25. [25]

      Di, J.; Zhao, X.; Lian, C.; Ji, M.; Xia, J.; Xiong, J.; Zhou, W.; Cao, X.; She, Y.; Liu, H.; et al. Nano Energy 2019, 61, 54. doi: 10.1016/j.nanoen.2019.04.029

  26. [26]

      Jiao, X.; Chen, Z.; Li, X.; Sun, Y.; Gao, S.; Yan, W.; Wang, C.; Zhang, Q.; Lin, Y.; Luo, Y.; et al. J. Am. Chem. Soc. 2017, 139, 7586. doi: 10.1021/jacs.7b02290

  27. [27]

      Xue, X.; Chen, R.; Chen, H.; Hu, Y.; Ding, Q.; Liu, Z.; Ma, L.; Zhu, G.; Zhang, W.; Yu, Q.; et al. Nano Lett. 2018, 18, 7372. doi: 10.1021/acs.nanolett.8b03655

  28. [28]

      Li, P.; Wang, F.; Wei, S.; Li, X.; Zhou, Y. Phys. Chem. Chem. Phys. 2017, 19, 4405. doi: 10.1039/C6CP08409E

  29. [29]

      Li, H.; Tsai, C.; Koh, A. L.; Cai, L.; Contryman, A. W.; Fragapane, A. H.; Zhao, J.; Han, H. S.; Manoharan, H. C.; Abild-Pedersen, F.; et al. Nat. Mater. 2016, 15, 48. doi: 10.1038/nmat4465

  30. [30]

      Xu, L.; Jiang, Q.; Xiao, Z.; Li, X.; Huo, J.; Wang, S.; Dai, L. Angew. Chem. Int. Ed. 2016, 55, 5277. doi: 10.1002/anie.201600687

  31. [31]

      Wu, J.; Li, X.; Shi, W.; Ling, P.; Sun, Y.; Jiao, X.; Gao, S.; Liang, L.; Xu, J.; Yan, W.; et al. Angew. Chem. Int. Ed. 2018, 57, 8719. doi: 10.1002/anie.201803514

  32. [32]

      Chen, X.; Liu, L.; Yu, P. Y.; Mao, S. S. Science 2011, 331, 746. doi: 10.1126/science.1200448

  33. [33]

      Zhao, Z.; Zhang, X.; Zhang, G.; Liu, Z.; Qu, D.; Miao, X.; Feng, P.; Sun, Z. Nano Res. 2015, 8, 4061. doi: 10.1007/s12274-015-0917-5

  34. [34]

      Zou, X.; Liu, J.; Su, J.; Zuo, F.; Chen, J.; Feng, P. Chem. - Eur. J. 2013, 19, 2866. doi: 10.1002/chem.201202833

  35. [35]

      Niu, P.; Yin, L. -C.; Yang, Y. -Q.; Liu, G.; Cheng, H. -M. Adv. Mater. 2014, 26, 8046. doi: 10.1002/adma.201404057

  36. [36]

      Li, X.; Sun, Y.; Xu, J.; Shao, Y.; Wu, J.; Xu, X.; Pan, Y.; Ju, H.; Zhu, J.; Xie, Y. Nat. Energy 2019, 4, 690. doi: 10.1038/s41560-019-0431-1

  37. [37]

      Lei, F.; Sun, Y.; Liu, K.; Gao, S.; Liang, L.; Pan, B.; Xie, Y. J. Am. Chem. Soc. 2014, 136, 6826. doi: 10.1021/ja501866r

  38. [38]

      Sun, Y.; Gao, S.; Lei, F.; Liu, J.; Liang, L.; Xie, Y. Chem. Sci. 2014, 5, 3976. doi: 10.1039/C4SC00565A

  39. [39]

      Sun, Y.; Liu, Q.; Gao, S.; Cheng, H.; Lei, F.; Sun, Z.; Jiang, Y.; Su, H.; Wei, S.; Xie, Y. Nat. Commun. 2013, 4, 2899. doi: 10.1038/ncomms3899

  40. [40]

      Xiong, Y.; Zhao, W.; Gu, D.; Tie, Z.; Zhang, W.; Jin, Z. Nano Lett. 2023, 23, 4876. doi: 10.1021/acs.nanolett.3c00524

  41. [41]

      Jiang, M.; Zhu, M.; Wang, M.; He, Y.; Luo, X.; Wu, C.; Zhang, L.; Jin, Z. ACS Nano 2023, 17, 3209. doi: 10.1021/acsnano.2c11046

  42. [42]

      Čížek, J. J. Mater. Sci. Technol. 2018, 34, 577. doi: 10.1016/j.jmst.2017.11.050

  43. [43]

      Gao, S.; Gu, B.; Jiao, X.; Sun, Y.; Zu, X.; Yang, F.; Zhu, W.; Wang, C.; Feng, Z.; Ye, B.; et al. J. Am. Chem. Soc. 2017, 139, 3438. doi: 10.1021/jacs.6b11263

  44. [44]

      Sun, Y.; Cheng, H.; Gao, S.; Liu, Q.; Sun, Z.; Xiao, C.; Wu, C.; Wei, S.; Xie, Y. J. Am. Chem. Soc. 2012, 134, 20294. doi: 10.1021/ja3102049

  45. [45]

      Wang, Z.; Zu, X.; Li, X.; Li, L.; Wu, Y.; Wang, S.; Ling, P.; Zhao, Y.; Sun, Y.; Xie, Y. Nano Res. 2022, 15, 6999. doi: 10.1007/s12274-022-4335-1

  46. [46]

      Shi, X.; Dong, X. A.; He, Y.; Yan, P.; Zhang, S.; Dong, F. ACS Catal. 2022, 12, 3965. doi: 10.1021/acscatal.2c00157

  47. [47]

      Liu, Y.; Xiao, C.; Li, Z.; Xie, Y. Adv. Energy Mater. 2016, 6, 1600436. doi: 10.1002/aenm.201600436

  48. [48]

      Sun, X.; Zhang, X.; Xie, Y. Matter 2020, 2, 842. doi: 10.1016/j.matt.2020.02.006

  49. [49]

      Jiang, M.; Zhu, M.; Wang, H.; Song, X.; Liang, J.; Lin, D.; Li, C.; Cui, J.; Li, F.; Zhang, X. L.; et al. Nano Lett. 2023, 23, 291. doi: 10.1021/acs.nanolett.2c04335

  50. [50]

      Gao, S.; Sun, Z.; Liu, W.; Jiao, X.; Zu, X.; Hu, Q.; Sun, Y.; Yao, T.; Zhang, W.; Wei, S.; et al. Nat. Commun. 2017, 8, 14503. doi: 10.1038/ncomms14503

  51. [51]

      Liang, L.; Ling, P.; Li, Y.; Li, L.; Liu, J.; Luo, Q.; Zhang, H.; Xu, Q.; Pan, Y.; Zhu, J.; et al. Sci. China Chem. 2021, 64, 953. doi: 10.1007/s11426-021-9967-9

  52. [52]

      Wang, H.; Bi, X.; Yan, Y.; Zhao, Y.; Yang, Z.; Ning, H.; Wu, M. Adv. Funct. Mater. 2023, 33, 2214946. doi: 10.1002/adfm.202214946

  53. [53]

      Jia, S.; Wu, L.; Xu, L.; Sun, X.; Han, B. Ind. Chem. Mater. 2023, 1, 93. doi: 10.1039/D2IM00056C

  54. [54]

      Wang, X.; Ma, S.; Liu, B.; Wang, S.; Huang, W. Chem. Commun. 2023, 59, 10044. doi: 10.1039/D3CC02843G

  55. [55]

      Zu, X.; Zhao, Y.; Li, X.; Chen, R.; Shao, W.; Wang, Z.; Hu, J.; Zhu, J.; Pan, Y.; Sun, Y.; et al. Angew. Chem. Int. Ed. 2021, 60, 13840. doi: 10.1002/anie.202101894

  56. [56]

      Liu, K.; Li, X.; Liang, L.; Wu, J.; Jiao, X.; Xu, J.; Sun, Y.; Xie, Y. Nano Res. 2018, 11, 2897. doi: 10.1007/s12274-017-1943-2

  57. [57]

      Ling, P.; Zhu, J.; Wang, Z.; Hu, J.; Zhu, J.; Yan, W.; Sun, Y.; Xie, Y. Nanoscale 2022, 14, 14023. doi: 10.1039/D2NR02364D

  58. [58]

      Zhu, S.; Li, X.; Jiao, X.; Shao, W.; Li, L.; Zu, X.; Hu, J.; Zhu, J.; Yan, W.; Wang, C.; et al. Nano Lett. 2021, 21, 2324. doi: 10.1021/acs.nanolett.1c00383

  59. [59]

      Zhu, J.; Shao, W.; Li, X.; Jiao, X.; Zhu, J.; Sun, Y.; Xie, Y. J. Am. Chem. Soc. 2021, 143, 18233. doi: 10.1021/jacs.1c08033

  60. [60]

      Jiao, X.; Zheng, K.; Liang, L.; Li, X.; Sun, Y.; Xie, Y. Chem. Soc. Rev. 2020, 49, 6592. doi: 10.1039/D0CS00332H

  61. [61]

      Chen, Z.; Concepcion, J. J.; Brennaman, M. K.; Kang, P.; Norris, M. R.; Hoertz, P. G.; Meyer, T. J. Proc. Natl. Acad. Sci. 2012, 109, 15606. doi: 10.1073/pnas.1203122109

  62. [62]

      Liang, L.; Li, X.; Sun, Y.; Tan, Y.; Jiao, X.; Ju, H.; Qi, Z.; Zhu, J.; Xie, Y. Joule 2018, 2, 1004. doi: 10.1016/j.joule.2018.02.019

  63. [63]

      Shi, J.; Cui, H. N.; Liang, Z.; Lu, X.; Tong, Y.; Su, C.; Liu, H. Energy Environ. Sci. 2011, 4, 466. doi: 10.1039/C0EE00309C

  64. [64]

      Kong, M.; Li, Y.; Chen, X.; Tian, T.; Fang, P.; Zheng, F.; Zhao, X. J. Am. Chem. Soc. 2011, 133, 16414. doi: 10.1021/ja207826q

  65. [65]

      Bi, W.; Ye, C.; Xiao, C.; Tong, W.; Zhang, X.; Shao, W.; Xie, Y. Small 2014, 10, 2820. doi: 10.1002/smll.201303548

  66. [66]

      Hou, J.; Cao, S.; Wu, Y.; Liang, F.; Sun, Y.; Lin, Z.; Sun, L. Nano Energy 2017, 32, 359. doi: 10.1016/j.nanoen.2016.12.054

  67. [67]

      Huygh, S.; Bogaerts, A.; Neyts, E. C. J. Phys. Chem. C 2016, 120, 21659. doi: 10.1021/acs.jpcc.6b07459

  68. [68]

      Shao, W.; Li, X.; Zhu, J.; Zu, X.; Liang, L.; Hu, J.; Pan, Y.; Zhu, J.; Yan, W.; Sun, Y.; et al. Nano Res. 2022, 15, 1882. doi: 10.1007/s12274-021-3789-x

  69. [69]

      Ye, F.; Zhang, S.; Cheng, Q.; Long, Y.; Liu, D.; Paul, R.; Fang, Y.; Su, Y.; Qu, L.; Dai, L.; et al. Nat. Commun. 2023, 14, 2040. doi: 10.1038/s41467-023-37679-3

  70. [70]

      Sun, Y.; Sun, Z.; Gao, S.; Cheng, H.; Liu, Q.; Piao, J.; Yao, T.; Wu, C.; Hu, S.; Wei, S.; et al. Nat. Commun. 2012, 3, 1057. doi: 10.1038/ncomms2066

  71. [71]

      Li, Z.; Cao, A.; Zheng, Q.; Fu, Y.; Wang, T.; Arul, K. T.; Chen, J. -L.; Yang, B.; Adli, N. M.; Lei, L.; et al. Adv. Mater. 2021, 33, 2005113. doi: 10.1002/adma.202005113

  72. [72]

      Zhang, B.; Zhang, J.; Hua, M.; Wan, Q.; Su, Z.; Tan, X.; Liu, L.; Zhang, F.; Chen, G.; Tan, D.; et al. J. Am. Chem. Soc. 2020, 142, 13606. doi: 10.1021/jacs.0c06420

  73. [73]

      Peng, C.; Luo, G.; Zhang, J.; Chen, M.; Wang, Z.; Sham, T. -K.; Zhang, L.; Li, Y.; Zheng, G. Nat. Commun. 2021, 12, 1580. doi: 10.1038/s41467-021-21901-1

  74. [74]

      Li, F.; Anjarsari, Y.; Wang, J.; Azzahiidah, R.; Jiang, J.; Zou, J.; Xiang, K.; Ma, H.; Arramel. Carbon Lett. 2023, 33, 1321. doi: 10.1007/s42823-022-00380-4

  75. [75]

      Wang, J.; Jiang, J.; Li, F.; Zou, J.; Xiang, K.; Wang, H.; Li, Y.; Li, X. Green Chem. 2023, 25, 32. doi: 10.1039/D2GC03160D

  76. [76]

      Wang, J.; Qin, Q.; Li, F.; Anjarsari, Y.; Sun, W.; Azzahiidah, R.; Zou, J.; Xiang, K.; Ma, H.; Jiang, J.; et al. Carbon Lett. 2023, 33, 1381. doi: 10.1007/s42823-022-00401-2

  77. [77]

      Lei, W.; Zhou, T.; Pang, X.; Xue, S.; Xu, Q. J. Mater. Sci. Technol. 2022, 114, 143. doi: 10.1016/j.jmst.2021.10.029

  78. [78]

      Wang, W.; Duan, J.; Liu, Y.; Zhai, T. Adv. Mater. 2022, 34, 2110699. doi: 10.1002/adma.202110699

  79. [79]

      Yang, S.; Jiang, M.; Zhang, W.; Hu, Y.; Liang, J.; Wang, Y.; Tie, Z.; Jin, Z. Adv. Funct. Mater. 2023, 33, 2301984. doi: 10.1002/adfm.202301984

  80. [80]

      Wang, S.; Hai, X.; Ding, X.; Chang, K.; Xiang, Y.; Meng, X.; Yang, Z.; Chen, H.; Ye, J. Adv. Mater. 2017, 29, 1701774. doi: 10.1002/adma.201701774

  81. [81]

      Luo, S.; Li, X.; Wang, M.; Zhang, X.; Gao, W.; Su, S.; Liu, G.; Luo, M. J. Mater. Chem. A 2020, 8, 5647. doi: 10.1039/D0TA01154A

•